KR100989198B1 - Process for reducing residual free radical polymerizable monomer content of polymers - Google Patents

Abstract

Disclosed are methods for reducing the residual free radical polymerizable monomer content of a polymer, comprising contacting the polymer in molten form with a free radical initiator such as di-t-amylperoxide.

Description

 PROCESS FOR REDUCING RESIDUAL FREE RADICAL POLYMERIZABLE MONOMER CONTENT OF POLYMERS}             

The present invention relates to a method for reducing the residual free radical polymerizable monomer content of a polymer.

It is known that many polymers can be produced, for example, by free radical polymerization processes. In this process, unreacted or residual monomer may remain at the end of the polymerization process. The presence of residual monomer materials may be undesirable for various reasons. For example, residual monomers may be characterized by toxic or unpleasant odors. Accordingly, there is a need to provide a process for reducing or removing residual free radical polymerizable monomers from polymers.

Summary of the Invention

The method of reducing the residual free radical polymerizable monomer content of the polymers of the present invention comprises free radical polymers in a molten form having a free radical polymerizable monomer content in an amount of 25 to 500 ppm (millions) based on the polymer. Contacting the initiator.

The method of reducing the residual free radical polymerizable monomer content of a polymer of the present invention comprises contacting a polymer in molten form having a free radical polymerizable monomer content with a free radical initiator present in an amount of 25 to 500 ppm based on the polymer. It includes.

More specifically, the process of the present invention is suitable for use in any polymer or interpolymer having a residual free radical polymerizable monomer content. Examples of monomers polymerizable by the free radical polymerization method include alpha-olefins; Dienes such as butadiene and chloroprene; Styrene, alpha-methyl styrene and the like; Heteroatom substituted alpha-olefins such as vinyl acetate, vinyl alkyl ethers such as ethyl vinyl ether, vinyltrimethylsilane, vinyl chloride, tetrafluoroethylene, chlorotrifluoroethylene, N- (3-dimethyl Aminopropyl) methacrylamide, dimethylaminopropyl methacrylamide, acrylamide, methacrylamide and similar derivatives; Acrylic acid and its derivatives such as acrylic acid, methacrylic acid, crotonic acid, acrylonitrile; Acrylic esters and similar derivatives substituted with methoxy, ethoxy, propoxy or butoxy, such as methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, methyl crotonate, glycidyl methacrylate , Alkyl crotonates and related esters; Cyclic and polycyclic olefin compounds such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and cyclic derivatives having up to 20 carbon atoms; Polycyclic derivatives such as norbornene and similar derivatives having up to 20 carbon atoms; Cyclic vinyl ethers such as 2,3-dihydrofuran, 3,4-dihydropyran and similar derivatives; Aryl alcohol derivatives such as vinylethylene carbonate, disubstituted olefins such as male compounds and fumar compounds such as male anhydride, diethyl fumarate and the like; And mixtures thereof, but is not limited thereto.

Examples of homopolymers or interpolymers having residual free radical polymerizable monomer content include polyethylene, poly (ethylene-alkylcrotonate) such as poly (ethylene-methyl crotonate), polystyrene, poly (ethylene-methylacrylate) , Poly (ethylene-butylacrylate), poly (ethylene-vinyl alcohol derivative) such as poly (ethylene-vinylacetate), poly (ethylene-vinyl chloride), poly (ethylene-tetrafluoroethylene), poly (ethylene- Norbornene), poly (ethylene-methylcrotonate), poly (ethylene-glycidyl methacrylate), poly (ethylene-methacrylamide), poly (ethylene-acrylonitrile), poly (ethylene-maleic anhydride ), Poly (ethylene-vinylethylene carbonate) and the like, but is not limited thereto. The interpolymer used in the preferred embodiment is available from Eastman Chemical Company as SP2260 poly (ethylene-methylacrylate) having a methyl acrylate content of 24% by weight and a melt index of 1.8 g / 10 min.

Free radical polymerization processes are known and include reactions initiated by the formation of free radicals from free radical generators such as peroxides or azo initiators. The reaction is initiated by the addition of free radicals to the unsaturated monomer molecules in a sequential manner in which they are added sequentially to further unsaturated monomers to form a growth chain or polymer. Reaction parameters such as pressure (typical running pressure for low density polyethylene (LDPE) is 10,000 to 40,000 psi or 1500 to 3000 atm) and temperature (typical running temperature for LDPE is 200 to 300 ° C.) change to result in product (See Kirk-Othmer Vol. 6, p. 383, "Encyclopedia of Chemical Technology" for further information).

In carrying out the process of the invention, the polymer with residual free radical polymerizable monomer content is heated to a temperature above the melting point of the polymer for melting the polymer. If the polymer is already in molten form, it is maintained at a temperature above the melting point of the polymer to keep the polymer in the molten state. The polymer in molten form is then contacted with the free radical initiator present in an amount of 25 to 500 ppm based on the polymer. As a result of this process, the residual free radical polymerizable monomer content of the polymer is reduced. In a preferred embodiment, the process is carried out in the presence of 50 to 300 ppm free radical initiator, based on the polymer, and in a more preferred embodiment in the presence of 90 to 150 ppm free radical initiator.

Any free radical initiator can be used to carry out the method of the invention. Free radical initiators are chemicals that initiate chemical reactions by generating free radicals. For further information, see Kirk Othmer, "Encyclopedia of Chemical Technology", Vol. 14, p.431. Suitable free radical initiators include, but are not limited to, the following examples:

1.Organic Peroxide (Heat Initiation Required):

a. t-alkyl peroxyester

   t-butyl peroxybenzoate

   t-butyl peroxyacetate

   t-butyl peroxy pivalate

   t-butyl peroxymaleate

b. Monoperoxycarbonate

   OO-t-butyl O-isopropyl monoperoxycarbonate

c. Diperoxyketal

   Ethyl 3,3-di- (t-amylperoxy) -butyrate

   n-butyl-4,4-di (t-butylperoxy)-valerate

   1,1-di (t-butylperoxy) -cyclohexane

   1,1-di (t-amylperoxy) -cyclohexane

d. Dialkyl peroxide

   2,5-di (t-butylperoxy) -2,5-dimethyl-3-hexyne

   2,5-di (t-butylperoxy) -2,5-dimethylhexane

   Di-t-amyl peroxide

   Di-t-butyl peroxide                 

   Dicumyl Peroxide

e. t-alkyl hydroperoxide

   t-butyl hydroperoxide

   t-amyl hydroperoxide

   Alpha-cumyl hydroperoxide

f. Ketone peroxide

   Methyl ethyl ketone peroxide

   Cyclohexane peroxide

   2,4-pentaneion peroxide

g. Others {G. Luft and H. Bitsch, J. Macromol. Sci. Chem. , A11 (6), 1089 (1977)]}

   Isobutyl Peroxide

   Isopropyl peroxydicarbonate

   Di-n-butyl peroxydicarbonate

   Di-s-butyl peroxydicarbonate

   t-butyl perneodecaneate

   Dioctylyl peroxide

   Diedecaneyl peroxide

   Dipropionyl Peroxide

   Diedecaneyl peroxide                 

   Dipropionyl peroxide

   Dilauroyl Peroxide

   t-butyl perisobutyrate

   t-butyl peracetate

   t-butyl per-3,5,5-trimethyl hexane

2. Azo compounds (heat initiation is required):

   2,2'-azobis [4-methoxy-2,4-dimethyl] pentanenitrile

   2,3'-azobis [2,4-dimethyl] pentanenitrile

   2,2'-azobis [isobutyronitrile]

3. Carbon-carbon initiator (thermal initiation is required):

   2,3-dimethyl-2,3-diphenylbutane

   3,4-dimethyl-3,4-diphenylhexane

   1,1,2,2-tetraphenyl-1,2-bis (trimethylsiloxy) ethane

4. Inorganic peroxide (thermal initiation required):

   Hydrogen peroxide

   Potassium peroxydisulfate

5. Photoinitiators (initiation by light is required):

   Benzophenone

   4-phenylbenzophenone

   Xanton                 

   Thioxanthone

   2-chlorothioxanthone

   4,4'-bis (N, N'-dimethylamino benzophenone) (Michler ketone)

   benzyl

   9,10-Penetraquinone

   9,10-anthraquinon

   Alpha, alpha-dimethyl-alpha-hydroxyacetophenone

   (1-hydroxycyclohexyl) -phenylmethaneone

   Benzoin ether

         methyl

         ethyl

         Isobutyl

   Alpha, alpha-dimethoxy-alpha-phenylacetophenone

   1-phenyl-1,2-propaneionone, 2- (O-benzoyl) oxime

   Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide

   Alpha-dimethylamino-alpha-ethyl-alpha-benzyl-3,5-dimethyl-4-morpholinoacetophenone.

In a preferred embodiment, di-t-amylperoxide is used as the free radical initiator.

The period for contacting the polymer with the free radical initiator carried out to reduce the residual free radical polymerizable monomer content of the polymer can be any period required to achieve a reduction in the monomer content capable of residual free radical polymerization. However, it is preferable that the contact of the polymer with the free radical initiator is completed within 10 minutes, more preferably to be completed within 5 seconds to 10 minutes. In this way, degradation of the polymer can be avoided.

The method of the invention can be carried out in any suitable apparatus. For example, the process of the invention may be preferably carried out using known reaction extrusion techniques. Such techniques include heating the polymer in an extruder to melt the polymer and mix the molten polymer with free radical initiators. Preferably a twin screw extruder is used as the extruder.

The invention will be more readily understood by reference to the following examples. Once the present invention has been fully disclosed, it is to be understood that many other forms of the invention may be apparent to those skilled in the art, and therefore the following examples are given by way of illustration only and limit the scope of the invention in any way. It is recognized that it should not be interpreted.

In the following examples, the test procedures described below were used to evaluate the properties of the polymers herein:

Melt Index-ASTM Test Method D-1238

Melt Index Ratio-ASTM Test Method D-1238                 

Residual Free Radical Polymerizable Monomer Content—Headspace Process Defined Below

Headspace Process for Determination of Residual Free Radical Polymerizable Comonomers in Polymer Pellets

The process of determining the residual comonomer (CM) in a copolymer by analyzing sample headspace using selective ion search (SIM) gas chromatography / mass spectroscopy (GC / MS) is summarized in this paragraph. For introduction into GC, volatiles were concentrated from the headspace of each sample using solid phase microextraction (SPME). SPME was performed using a passive fiber support containing 75 μm carboxyl / polydimethylsiloxane fibers (Supelco chromatography product). Approximately 10 g of polymer pellets were accurately weighed and sealed in 40 ml glass containers with septum caps. The fibers were exposed to the headspace of the glass vessel at 60 ° C. for 60 minutes and then the pellets were equilibrated at 60 ° C. for 24 hours. Samples were analyzed for 0.3 minutes by GC / MS using the apparatus described below with inlets operating in non-dividing mode during injection. Data was collected using HP 5890 Series II gas chromatography with Hewlett-Packard (HP) 5989 mass selection detector. Separation was performed on a DB-5ms (J & W) column (30m × 0.25mm inner diameter, 10μm film thickness) using the following oven profile: 30 ° C. (2 min, hold) → 160 at a rate of 10 ° C./min. ° C (no maintenance). The mass selection detector was operated at 70 eV using electron impact ionization and scanned by SIM method for ions of 27, 42, 55 and 85 amu. A hold time of 100 milliseconds was used for each mass shifted to 2.13 capture cycles / second.

The concentration of residual CM in the sample headspace was calculated using the CM peak area integrated from the ion chromatogram extracted for m / z 55 and the response factor determined from gas standards of known CM concentration in nitrogen. Standards range in concentration from 0 to 9.6 nanograms CM per ml of nitrogen. The volume V _HS of the headspace of each glass container from the weight of the pellet and the density of the polymer was calculated to give the total amount of CM in the headspace as the product of [CM] _HS and V _HS . It was assumed that upon extended heating at 60 ° C., the CM originally present in the pellet was substantially all led to the headspace. Therefore, the concentration of CM in the polymer was measured by dividing the total amount of CM by the weight of the polymer sample.

Examples 1 to 3

In Examples 1 to 3, the process was carried out under the same conditions except for the amount of di-t-amylperoxide added as polymer and free radical initiator. More specifically, the process was carried out using a Berstorff ZE-25, 33L / D (length / diameter) twin screw extruder, where all zones were equilibrated at a temperature of about 175 ° C. After equilibration for about 45 minutes, SP2260 ethylene-methyl acrylate interpolymers with 24 wt% methyl acrylate content and 1.8 g / 10 min melt index, available from Eastman Chemical Company, were introduced at various rates. A di-t-amylperoxide free radical initiator (dissolved in petroleum ether) was introduced at a rate such that the polymer was in contact with sufficient free radical initiator to achieve a reduction in the residual free radical polymerizable monomer content of the polymer. The SP2260 interpolymer having a residual methyl acrylate content above 100 ppm was contacted with the free radical initiator. In each of Examples 1-3, it was determined that the residence time for contact of the polymer with the free radical initiator was about 25-30 seconds by calculating the time required for the colored pellets to pass through the extruder. The polymer strand obtained from the extruder was cooled in a bucket and then cut into small pellets. The properties of the obtained polymer pellets are shown in Table 1 below.

Example 1

The SP2260 interpolymer was introduced at a rate of about 6 lb / hr and the di-t-amyl peroxide was introduced at a rate that allowed the polymer to contact about 150 ppm of the di-t-amyl peroxide.

Example 2

The SP2260 interpolymer was introduced at a rate of about 8 lb / hr and the di-t-amyl peroxide was introduced at a rate that caused the polymer to contact about 112 ppm of the di-t-amyl peroxide.

Example 3

The SP2260 interpolymer was introduced at a rate of about 10 lb / hr and the di-t-amyl peroxide was introduced at a rate that caused the polymer to contact about 90 ppm of the di-t-amyl peroxide.

The results obtained by performing Examples 1 to 3 as described above are shown in Table 1 below.                 

From the data in Table 1, it was observed that the process of the present invention achieves a significant reduction in the residual free radical polymerizable monomer content of the polymer. As another useful feature, the method of the present invention does not substantially change the other physical properties of the polymer.

It is to be understood that the forms of the invention disclosed herein are for illustrative purposes only and are not intended to limit the scope of the invention. The present invention includes all modifications falling within the scope of the following claims.

Claims (13)

A method of reducing the residual free radical polymerizable monomer content of a polymer comprising contacting the polymer in molten form with a free radical initiator present in an amount of from 25 to 500 ppm based on the polymer. The method of claim 1, The free radical initiator is present in an amount from 50 to 300 ppm. The method of claim 2, Wherein the free radical initiator is present in an amount of 90 to 150 ppm. The method of claim 1, The free radical initiator is selected from the group consisting of organic peroxides, azo compounds, carbon-carbon initiators, inorganic peroxides, and photoinitiators. The method of claim 4, wherein The free radical initiator is an organic peroxide. The method of claim 5, The free radical initiator is di-t-amylperoxide. The method of claim 1, The melted form of the polymer is contacted with the free radical initiator for a period of up to 10 minutes. The method of claim 1, The polymer is an ethylene-methyl acrylate interpolymer. The method of claim 1, The method of reducing the residual free radical polymerizable monomer content is carried out in an extruder. The method of claim 9, The extruder is a twin screw extruder. The method of claim 10, The polymer is an ethylene-methyl acrylate interpolymer, the polymer in molten form is contacted with the free radical initiator for a period of up to 10 minutes, and the di-t- in which the free radical initiator is present in an amount of 90 to 150 ppm based on the polymer. The method is amyperperoxide. The method of claim 1, The polymer in molten form is contacted with the free radical initiator for a period of up to 5 seconds to 10 minutes. The method of claim 11, The polymer in molten form is contacted with di-t-amylperoxide for a period of up to 5 seconds up to 10 minutes.